CN116917407A - Thermoplastic resin composition and molded product using the same - Google Patents
Thermoplastic resin composition and molded product using the same Download PDFInfo
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- CN116917407A CN116917407A CN202280016679.6A CN202280016679A CN116917407A CN 116917407 A CN116917407 A CN 116917407A CN 202280016679 A CN202280016679 A CN 202280016679A CN 116917407 A CN116917407 A CN 116917407A
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- acrylate
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 63
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 31
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 30
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 25
- 239000011258 core-shell material Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 239000011787 zinc oxide Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- -1 acrylic ester Chemical class 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 claims description 7
- 238000005424 photoluminescence Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000004609 Impact Modifier Substances 0.000 claims description 2
- 239000012963 UV stabilizer Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- LUECERFWADIZPD-UHFFFAOYSA-N 1-tert-butyl-2-ethenylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1C=C LUECERFWADIZPD-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
There is provided a thermoplastic resin composition comprising 100 parts by weight of a polyalkyl (meth) acrylate resin based on (A); (B) 1 to 3 parts by weight of a core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell; (C) 2 to 5 parts by weight of a silicone polyester copolymer; and (D) 1 to 5 parts by weight of zinc oxide (ZnO).
Description
Technical Field
The present invention relates to a thermoplastic resin composition and a molded product using the same.
Background
Recently, thermoplastic resins widely used in electric/electronic products, automobiles, construction materials, leisure articles, and the like have rapidly replaced conventional glass or metal regions. Accordingly, there is an increasing demand for thermoplastic resins capable of implementing excellent impact resistance, water resistance, scratch resistance and antibacterial properties.
In particular, as the technological trend of sharing vehicles such as electric vehicles and automatic driving vehicles is changed, the perception of the interior of the vehicles is being changed into living space, not space for driving only. Interior materials are being introduced, and the use of antibacterial/antifungal materials as interior materials is required.
In order to introduce antibacterial/antifungal materials as interior materials, various methods such as an anti-fouling (anti-fouling) coating, an antibacterial additive, or an antistatic additive have been tried in order to fundamentally prevent contamination of unpainted materials used in automobile interior parts and to maintain safe sanitary conditions.
However, in the case of the scratch resistant material or the antibacterial material known so far, the additive is generally eluted to the surface of the material to exhibit characteristics, and it is difficult to maintain permanent characteristics since the scratch resistance or antibacterial characteristics are imparted by applying a polymeric or inorganic material.
Therefore, it is required to study a thermoplastic resin composition having excellent scratch resistance and antibacterial properties.
Disclosure of Invention
Technical problem
Embodiments provide a thermoplastic resin composition having excellent scratch resistance, abrasion resistance, water resistance, chemical resistance, and antibacterial properties, and a molded product using the same.
Technical proposal
According to an embodiment, there is provided a thermoplastic resin composition including: based on (a) 100 parts by weight of a polyalkyl (meth) acrylate resin, (B) 1 to 3 parts by weight of a core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell; (C) 2 to 5 parts by weight of a silicone polyester copolymer; and (D) 1 to 5 parts by weight of zinc oxide (ZnO).
(A) The polyalkyl (meth) acrylate resin may have a glass transition temperature (Tg) of 100 to 150 ℃.
(A) The weight average molecular weight of the polyalkyl (meth) acrylate resin may be 50,000g/mol to 200,000g/mol.
(A) The polyalkyl (meth) acrylate resin may be a polymethyl methacrylate resin.
(B) The core-shell copolymer comprising an acrylate rubber polymer core and a (meth) acrylate shell may be a core-shell copolymer comprising: an acrylic rubber polymer core wherein a C1 to C20 linear alkyl acrylate monomer and an aromatic vinyl monomer are crosslinked; and a shell in which the (meth) acrylic acid ester compound is graft-copolymerized on the acrylic acid ester rubber polymer core.
(B) The core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell may be a core-shell copolymer in which polymethyl methacrylate forms a shell on a butyl acrylate-styrene crosslinked copolymer core.
The average particle diameter of the acrylic rubber polymer may be 0.5 μm to 5.0 μm.
(C) The siloxane polyester copolymer may be represented by chemical formula 1.
[ chemical formula 1]
In chemical formula 1, R 1 、R 2 、R 3 And R is 4 Each independently is an alkylene group having 1 to 5 carbon atoms, and m and n are integers greater than or equal to 1.
(D) The zinc oxide may have an average particle size of 0.5 μm to 3 μm and 1m 2 /g to 10m 2 BET specific surface area per gram.
(D) Zinc oxide has a peak position 2 theta value of 35 to 37 deg. in X-ray diffraction (XRD) analysis, and has a peak position 2 theta value according to equation 1To->Crystallite size values of (a).
[ equation 1]
In equation 1, k is a shape factor, λ is an X-ray wavelength, β is a FWHM value of an X-ray diffraction peak, and θ is a peak position value (peak position degree).
When photoluminescence is measured, the (D) zinc oxide may have a size ratio (B/a) of 0.01 to 1 between peak a of 370nm to 390nm and peak B of 450nm to 600 nm.
The thermoplastic resin composition may further comprise (E) an acrylic rubber-modified vinyl-based graft copolymer.
(E) The weight ratio of the acrylic rubber modified vinyl graft copolymer to the (A) polyalkyl (meth) acrylate resin may be 1:1.5 to 1:4.
The thermoplastic resin composition may further include at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, and dyes.
In another embodiment, a molded product made from the thermoplastic resin composition is provided.
Advantageous effects
It is possible to provide a thermoplastic resin composition having excellent scratch resistance, abrasion resistance, water resistance, chemical resistance and antibacterial properties, and a molded product manufactured therefrom.
Detailed Description
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto and the invention is defined by the scope of the claims.
In the present specification, unless otherwise mentioned, "copolymerization" means block copolymerization, random copolymerization or graft copolymerization, and "copolymer" means a block copolymer, a random copolymer or a graft copolymer.
In the present specification, unless otherwise mentioned, the average particle diameter of the rubber polymer means a volume average diameter, and means a Z-average particle diameter measured using a dynamic light scattering analyzer.
In the present specification, unless otherwise mentioned, the average particle diameter of zinc oxide is a particle diameter (D50) corresponding to 50% by weight in the particle size distribution curve of individual particles (particles do not aggregate to form secondary particles), which is measured by using a particle size analyzer (laser diffraction particle size analyzer LS13 320,Beckman Coulter company).
In the present specification, unless otherwise mentioned, the weight average molecular weight is measured by dissolving a powder sample in an appropriate solvent and then performing Gel Permeation Chromatography (GPC) with a 1200 series manufactured by Agilent Technologies company (standard sample is polystyrene manufactured by Shodex).
In the present specification, unless otherwise mentioned, the specific surface area of zinc oxide was measured using a BET analysis apparatus (surface area and porosity analyzer ASAP 2020,Micromeritics Instruments company) using a nitrogen gas adsorption method.
The thermoplastic resin composition according to an embodiment includes: based on 100 parts by weight of (A) a polyalkyl (meth) acrylate resin; (B) 1 to 3 parts by weight of a core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell; (C) 2 to 5 parts by weight of a silicone polyester copolymer; and (D) 1 to 5 parts by weight of zinc oxide (ZnO).
Hereinafter, each component included in the thermoplastic resin composition will be described in detail.
(A) Poly (meth) acrylic acid alkyl ester resin
The thermoplastic resin composition according to the embodiment includes (a) a poly (meth) acrylic acid alkyl ester resin. (A) The polyalkyl (meth) acrylate resin may impart scratch resistance to the thermoplastic resin composition.
(A) The polyalkyl (meth) acrylate resin may be a polymer of a C1 to C10 alkyl (meth) acrylate or a combination thereof.
(A) The polyalkyl (meth) acrylate resin can be obtained by polymerizing a raw material monomer by a known polymerization method such as suspension polymerization, bulk polymerization or emulsion polymerization.
(A) The polyalkyl (meth) acrylate resin may have a glass transition temperature (Tg) of 100 ℃ to 150 ℃, for example 110 ℃ to 130 ℃.
(A) The polyalkyl (meth) acrylate resin may have a weight average molecular weight of 50,000g/mol to 200,000g/mol, for example 70,000g/mol to 150,000 g/mol. When the weight average molecular weight of the (a) polyalkyl (meth) acrylate resin satisfies the above range, the thermoplastic resin composition including the polyalkyl (meth) acrylate resin may exhibit excellent scratch resistance and flowability.
(A) The polyalkyl (meth) acrylate resin may be a polymethyl methacrylate resin. The polymethyl methacrylate resin may be a copolymer of a monomer mixture including 80 to 99wt% of methyl methacrylate and 1 to 20wt% of methyl acrylate.
(B) Core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell
The thermoplastic resin composition according to the embodiment includes (B) a core-shell copolymer including an acrylic rubber polymer core and a (meth) acrylic shell. (B) Core-shell copolymers having an acrylate rubber polymer core- (meth) acrylate shell structure are used to enhance various physical properties of thermoplastic resin compositions, such as impact resistance, mechanical properties, and appearance properties.
In an embodiment, in (B) a core-shell copolymer comprising an acrylate rubber polymer core and a (meth) acrylate shell, the (meth) acrylate polymer is graft-copolymerized on the acrylate rubber polymer core to form the shell.
The acrylic rubber polymer may be a crosslinked polymer of acrylic monomers that are C1 to C20 linear or C1 to C20 branched alkyl esters of acrylic acid (such as ethyl acrylate or butyl acrylate), C3 to C20 cycloalkyl esters of acrylic acid, C1 to C20 linear or C2 to C20 branched alkyl esters of methacrylic acid, C3 to C20 cycloalkyl esters of methacrylic acid, or combinations thereof, and may be a crosslinked copolymer of an acrylic monomer and one or more aromatic vinyl monomers capable of free radical polymerization therewith.
In the crosslinked copolymer of the acrylic monomer and the at least one aromatic vinyl monomer capable of free radical polymerization with the acrylic monomer, the weight of the component derived from the aromatic vinyl monomer may be 1 to 20wt%, for example, 5 to 20wt%, based on the total weight of the acrylic rubber polymer core.
The aromatic vinyl monomer may be styrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, a-methylstyrene, o-t-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, or combinations thereof.
The (meth) acrylic acid ester compound constituting the (meth) acrylic acid ester shell may be a methacrylate ester, an acrylic acid ester, a methyl methacrylate, a methyl acrylate, an ethyl methacrylate, an ethyl acrylate, a propyl methacrylate, a propyl acrylate, a butyl methacrylate, a butyl acrylate, or a combination thereof.
In an embodiment, (B) a core-shell copolymer comprising an acrylate rubber polymer core and a (meth) acrylate shell may be a core-shell copolymer comprising: an acrylic rubber polymer core wherein a C1 to C20 linear alkyl acrylate monomer and an aromatic vinyl monomer are crosslinked; and a shell in which the (meth) acrylic compound is graft-copolymerized on the acrylic rubber polymer core.
(B) The core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell may comprise 40wt% to 80wt% of the acrylic rubber polymer core, and 20wt% to 60wt% of the (meth) acrylic shell. Within the above weight range, the weather resistance and impact resistance of the thermoplastic resin composition can be improved.
In embodiments, (B) the core-shell copolymer comprising an acrylate rubber polymer core and a (meth) acrylate shell may be a core-shell copolymer in which polymethyl methacrylate forms a shell on a butyl acrylate-styrene cross-linked copolymer core.
In embodiments, the average particle size of the (B) acrylate rubber polymer core may be 0.5 μm to 5.0 μm, such as 1.0 μm to 3.0 μm, such as 1.0 μm to 2.0 μm. Within these ranges, the thermoplastic resin composition may have excellent impact resistance and scratch resistance.
In embodiments, the amount of the (B) core-shell copolymer including the acrylate rubber polymer core and the (meth) acrylate shell may be 1 to 3 parts by weight, for example, 1 to 2 parts by weight, based on 100 parts by weight of the (a) polyalkyl (meth) acrylate resin. Within these ranges, the thermoplastic resin composition may have excellent impact resistance and scratch resistance.
(C) Silicone polyester copolymers
The thermoplastic resin composition according to the embodiment may include (C) a silicone polyester copolymer. (C) The silicone polyester copolymer can improve scratch resistance of the thermoplastic resin composition.
(C) The silicone polyester copolymer can be represented by chemical formula 1:
[ chemical formula 1]
In chemical formula 1, R 1 、R 2 、R 3 And R is 4 Independently an alkylene group having 1 to 5 carbon atoms, m and n are integers greater than or equal to 1.
In an embodiment, in chemical formula 1, R 1 And R is 2 Can be- (CH) 2 ) 3 -，R 3 And R is 4 Can be- (CH) 2 ) 5 And m and n may be integers of 1 or greater satisfying m: n=18:30.
The silicone polyester copolymer (C) may be included in an amount of 2 to 5 parts by weight, for example, 2 to 4 parts by weight, based on 100 parts by weight of the (A) polyalkyl (meth) acrylate resin. Within this weight part, the thermoplastic resin composition may have excellent scratch resistance and impact resistance.
(D) Zinc oxide
The thermoplastic resin composition according to the embodiment may include (D) zinc oxide. (D) Zinc oxide plays a role in imparting antibacterial properties to the thermoplastic resin composition and molded products produced therefrom, and also plays a role in improving abrasion resistance and appearance characteristics.
In embodiments, (D) zinc oxide may have an average particle size of 0.5 μm or greater, such as 0.8 μm or greater, such as 1 μm or greater, and such as 3 μm or less, such as 2.5 μm or less, such as 2 μm or less, such as 0.5 μm to 3 μm, such as 0.5 μm to 2.5 μm, such as 0.5 μm to 2 μm, such as 0.8 μm to 2 μm. Within the above average particle diameter range, the antibacterial property and appearance characteristics of the thermoplastic resin composition and molded products produced therefrom can be improved.
(D) The zinc oxide may have a particle size of 1m 2 /g or greater, e.g. 10m 2 /g or less, e.g. 9m 2 /g or less, e.g. 8m 2 /g or less, e.g. 7m 2 /g or less, e.g. 1m 2 /g to 10m 2 /g, e.g. 1m 2 /g to 7m 2 BET specific surface area per gram. Within the range of the BET specific surface area, the antibacterial property, light resistance and weather resistance of the thermoplastic resin composition and molded products produced therefrom can be improved.
The purity of zinc oxide (D) measured by weight may be 99% or more using TGA thermal analysis maintained at a temperature of 800 ℃.
When analyzed by X-ray diffraction (XRD), and based on the measured FWHM value (full width at half maximum of diffraction peak), (D) zinc oxide has a peak position 2θ value in the range of 35 ° to 37 °, the crystallite size value calculated by applying the Scherrer equation expressed by equation 1 isTo->For example 1,200 to->For example 1,300 to->For example 1,300 to->
[ equation 1]
In equation 1, k is a shape factor, λ is an X-ray wavelength, β is a FWHM value of an X-ray diffraction peak, and θ is a peak position value (peak position degree).
Specifically, the crystallite size can be measured using a high resolution X-ray diffractometer (XRD, manufacturer: X' pert, device name: PRO-MRD), and can be measured irrespective of sample type (e.g., powder form, injection molded sample). On the other hand, in the case of using an injection molded sample, XRD analysis may be performed after heat treatment at 600 ℃ for 2 hours under air condition to remove residual polymer for more accurate analysis.
Within the above-mentioned crystallite size range, the antibacterial property, light resistance and weather resistance of the thermoplastic resin composition and molded products produced therefrom can be improved.
(D) The zinc oxide may have various shapes, such as a spherical shape, a plate shape, a rod shape, and combinations thereof. In an embodiment, the zinc oxide may have various shapes other than a needle shape, such as a spherical shape, a plate shape, a rod shape, and the like.
When measuring Photoluminescence (PL), the (D) zinc oxide has a size ratio (B/a) between peak a in the region of 370nm to 390nm and peak B in the region of 450nm to 600nm, i.e. a PL size ratio of 0.01 to 1, for example 0.1 to 0.5.
In photoluminescence measurement, first, zinc oxide powder was put into a granulator having a diameter of 6mm and compressed to prepare a measurement sample in a flat state, the measurement sample was irradiated with incident he—cd laser (KIMMON co.,30 mW), an emission spectrum was detected using a CCD detector, and at this time, the temperature of the CCD detector was maintained at-70 ℃. Within the above range, the thermoplastic resin composition and molded articles prepared therefrom can exhibit excellent antibacterial properties, light resistance, weather resistance, and the like.
Within the above range, the thermoplastic resin composition and molded articles prepared therefrom can exhibit excellent antibacterial properties, light resistance, weather resistance, and the like.
(D) Zinc oxide can be prepared by: zinc in molten metal form is heated to 850 ℃ to 1,000 ℃, e.g., 900 ℃ to 950 ℃ to evaporate it, oxygen is injected, cooled to 20 ℃ to 30 ℃, and then heated at 400 ℃ to 900 ℃, e.g., 500 ℃ to 800 ℃, e.g., 30 minutes to 150 minutes, e.g., 60 minutes to 120 minutes.
The zinc (D) oxide may be included in an amount of 1 to 5 parts by weight, for example, 2 to 4 parts by weight, based on 100 parts by weight of the (a) polyalkyl (meth) acrylate resin. Within the above-mentioned weight part range, the antibacterial property, light resistance, appearance characteristics and impact resistance of the thermoplastic resin composition and molded products produced therefrom can be improved.
(E) Acrylic rubber modified vinyl graft copolymer
In addition to the above components (a) to (D), the thermoplastic resin composition according to the embodiment may further include (E) an acrylic rubber-modified vinyl-based graft copolymer.
The acrylic rubber modified vinyl-based graft copolymer may be prepared according to any preparation method known to those skilled in the art, and the preparation method may include conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. As a non-limiting example, it may be prepared by a method comprising: an acrylic rubber polymer is prepared, and then a vinyl compound including an aromatic vinyl compound and a vinyl cyanide compound is graft polymerized on a core formed of one or more layers of the acrylic rubber polymer to form one or more shell layers.
The acrylic rubber polymer may be prepared using an acrylic monomer as a main monomer. The acrylic monomer may be one or more selected from ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and hexyl acrylate, but is not limited thereto.
The acrylic monomer may be copolymerized with one or more other monomers that are free radically polymerizable. When copolymerized, the amount of the one or more other free-radically polymerizable monomers may be from 5wt% to 30wt%, such as from 10wt% to 20wt%, based on the total weight of the acrylate rubber polymer.
In embodiments, the average particle size of the acrylate rubber polymer may be greater than or equal to 100nm, such as less than or equal to 500nm, such as less than or equal to 450nm, such as less than or equal to 400nm, such as less than or equal to 350nm, such as less than or equal to 300nm, such as less than or equal to 250nm, such as less than or equal to 200nm, such as 100nm to 500nm, such as 100nm to 450nm, such as 100nm to 400nm, such as 100nm to 350nm, such as 100nm to 300nm, such as 100nm to 250nm, or such as 100nm to 200nm. Within the above particle size range, the thermoplastic resin composition may have excellent overall mechanical properties such as impact resistance and tensile strength, flowability and processability.
The aromatic vinyl compound included in the shell layer may be at least one selected from the group consisting of styrene, α -methylstyrene, p-t-butylstyrene, 2, 4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene, but is not limited thereto, and the vinyl cyanide compound included in the shell layer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and fumaronitrile, but is not limited thereto.
The acrylate rubber polymer may be 40wt% to 60wt%, such as 45wt% to 55wt%, based on the total weight of the acrylate rubber modified vinyl graft copolymer.
In embodiments, the acrylic rubber modified vinyl-based graft copolymer may be an acrylate-styrene-acrylonitrile graft copolymer.
(E) The weight ratio of the acrylic rubber modified vinyl graft copolymer to the (A) polyalkyl (meth) acrylate resin may be 1:1.5 to 1:4. Within the above weight ratio range, the impact resistance of the thermoplastic resin composition can be improved.
(F) Additive agent
In addition to components (a) to (E), the thermoplastic resin composition according to the embodiment may further include one or more additives required for balancing physical properties while exhibiting excellent scratch resistance, abrasion resistance and antibacterial properties, or one or more additives required according to the end use of the thermoplastic resin composition.
Specifically, the additive may include at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet (UV) stabilizers, pigments, dyes, and the like, which may be used alone or in combination of two or more.
These additives may be appropriately included within a range that does not impair physical properties of the thermoplastic resin composition, and specifically, the amount included may be less than or equal to 20 parts by weight based on 100 parts by weight of (a) the polyalkyl (meth) acrylate resin, but is not limited thereto.
On the other hand, the thermoplastic resin composition according to the embodiment may be mixed with and used together with other resins or other rubber components.
Another embodiment provides a molded product produced using the thermoplastic resin composition according to the embodiment. The thermoplastic resin composition may be used to produce molded products by various methods known in the art, such as injection molding and extrusion molding.
Hereinafter, the present invention will be explained in more detail with reference to examples. However, these examples should in no way be construed as limiting the scope of the invention.
Examples 1 to 5 and comparative examples 1 to 6
Thermoplastic resin compositions of examples 1 to 5 and comparative examples 1 to 6 were prepared according to the component content ratios described in table 1, respectively.
Specifically, the components described in table 1 were quantitatively and continuously introduced into a feeding stage of a twin-screw extruder (L/d=44, Φ=35 mm), and melted/kneaded at about 260 ℃, to prepare each thermoplastic resin composition in the form of pellets. Subsequently, after drying the thermoplastic resin composition at about 80 ℃ for about 2 hours, samples for physical properties and gloss were prepared by using a 6 oz injection molding machine set at a cylinder temperature of about 250 ℃ and a mold temperature of about 60 ℃. The measured characteristics are shown in tables 2 and 3.
In table 1, the contents of the components (B) to (D) are expressed in parts by weight based on 100 parts by weight of the component (a), but in examples 5, comparative examples 5 and 6 including the component (E), the contents of the components (B) to (D) are expressed in parts by weight based on 100 parts by weight of the components (a) and (E).
TABLE 1
Each component described in table 1 is as follows.
(A) Poly (meth) acrylic acid alkyl ester resin
Polymethyl methacrylate resins (V040, armema) having a glass transition temperature (Tg) of about 120 ℃ were used.
(B) Core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell
A core-shell copolymer is used having a butyl acrylate-styrene crosslinked copolymer core and a polymethyl methacrylate shell formed thereon and comprising about 50wt% butyl acrylate-styrene crosslinked copolymer core and about 50wt% polymethyl methacrylate shell.
(C) Silicone polyester copolymers
Using a compound represented by chemical formula 2H-Si 6441P，Evonik Ind.)：
[ chemical formula 2]
(D) Zinc oxide
KS-1 from Hanil Chemical Ind. Co., ltd was used.
(E) Acrylic rubber modified vinyl-based graft copolymer
A core-shell copolymer is used which is prepared by forming a styrene-acrylonitrile copolymer shell on a butyl acrylate-styrene cross-linked copolymer core and comprises about 50wt% butyl acrylate-styrene cross-linked copolymer core and about 50wt% styrene-acrylonitrile copolymer shell, wherein the average particle size of the core is about 250nm.
Evaluation of physical Properties
The physical property evaluation results are shown in tables 2 and 3.
(1) Abrasion resistance: after rubbing a sample surface having a size of 100mm×100mm×3.2mm 10 times with white cotton cloth, the glossiness at 20 ° reflection angle before and after rubbing was measured according to ASTM D523, and the glossiness retention was calculated. At this time, if the initial gloss is 100GU and the gloss after rubbing is 80GU, the gloss retention is defined as 80%. Since the sample wears more severely after rubbing, its gloss changes more, and therefore it is considered that the higher the gloss retention, the more excellent the abrasion resistance.
(2) Scratch resistance: scratch resistance was compared by measuring the brightness change value (δl) on the surface of the sample before/after scratch evaluation with an Erichsen scratch resistance tester, and the scratch resistance of the sample having dimensions of 100mm×100mm×3.2mm was evaluated. When a sample is scratched, it is considered that the higher δl is, the lower scratch resistance is, because of occurrence of fine cracks on the sample surface and thus increase in brightness.
(3) Water resistance: izod impact strength was measured according to ASTM D256 before/after 300 hours of room placement at 60℃and 95% Relative Humidity (RH) for a 1/8 inch notched specimen for impact strength, and was used to calculate the impact strength retention. The higher the impact strength retention, the more excellent the water resistance is considered.
(4) Chemical resistance: after placing an ASTM D638 type I sample on a jig having a critical strain of 2.1%, alcohol was applied thereto, and left at room temperature for 168 hours, whether or not cracks occurred was checked with naked eyes.
(5) Heat resistance: vicat Softening Temperature (VST) was measured according to the evaluation method specified in ISO 306.
(6) Evaluation of antibacterial Properties
The antibacterial activity of each sample was measured by inoculating staphylococcus aureus (ATCC 6538P) and escherichia coli (ATCC 8739) into the samples and culturing them at 35±1 ℃ and 90% Relative Humidity (RH) for 24 hours according to the evaluation method of JIS Z2801 antibacterial. An antibacterial effect is considered to be present when the antibacterial activity is 2.0 or more.
After the evaluation of water resistance and chemical resistance, each sample was wiped 5 times with distilled water and a sponge, and then dried for 24 hours.
TABLE 2
TABLE 3 Table 3
Referring to tables 1 to 3, the thermoplastic resin compositions of examples exhibited excellent abrasion resistance, scratch resistance, water resistance, chemical resistance, heat resistance, and antibacterial properties as compared to the thermoplastic resin compositions of comparative examples.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (15)
1. A thermoplastic resin composition comprising:
based on 100 parts by weight of (A) a polyalkyl (meth) acrylate resin;
(B) 1 to 3 parts by weight of a core-shell copolymer comprising an acrylic rubber polymer core and a (meth) acrylic shell;
(C) 2 to 5 parts by weight of a silicone polyester copolymer; and
(D) 1 to 5 parts by weight of zinc oxide (ZnO).
2. The thermoplastic resin composition according to claim 1, wherein the polyalkyl (meth) acrylate resin (a) has a glass transition temperature (Tg) of 100 ℃ to 150 ℃.
3. The thermoplastic resin composition according to claim 1 or claim 2, wherein the weight average molecular weight of the polyalkyl (meth) acrylate resin (a) is 50,000g/mol to 200,000g/mol.
4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein (a) the polyalkyl (meth) acrylate resin is a polymethyl methacrylate resin.
5. The thermoplastic resin composition according to any one of claim 1 to claim 4, wherein (B) said core-shell copolymer comprising said acrylic rubber polymer core and said (meth) acrylic ester shell is a core-shell copolymer comprising: an acrylic rubber polymer core wherein a C1 to C20 linear alkyl acrylate monomer and an aromatic vinyl monomer are crosslinked; and a shell in which a (meth) acrylic compound is graft-copolymerized on the acrylic rubber polymer core.
6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the core-shell copolymer shell comprising the acrylic rubber polymer core and (B) the (meth) acrylate is a core-shell copolymer in which polymethyl methacrylate forms a shell on a butyl acrylate-styrene crosslinked copolymer core.
7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the average particle diameter of the acrylic rubber polymer is 0.5 μm to 5.0 μm.
8. The thermoplastic resin composition of any one of claims 1 to 7, wherein (C) the silicone polyester copolymer is represented by chemical formula 1:
[ chemical formula 1]
Wherein, in chemical formula 1, R 1 、R 2 、R 3 And R is 4 Independently an alkylene group having 1 to 5 carbon atoms, m and n are integers greater than or equal to 1.
9. The thermoplastic resin composition according to any one of claims 1 to 8, wherein (D) the zinc oxide has an average particle diameter of 0.5 μm to 3 μm and a BET specific surface area of 1m 2 /g to 10m 2 /g。
10. The thermoplastic resin composition of any one of claims 1 to 9, wherein (D) the zinc oxide has a peak position 2Θ value of 35 ° to 37 ° in X-ray diffraction (XRD) analysis, and a crystallite size value of according to equation 1To->
[ equation 1]
Where in equation 1, k is a shape factor, λ is an X-ray wavelength, β is a FWHM value of an X-ray diffraction peak, and θ is a peak position value (peak position degree).
11. The thermoplastic resin composition of any one of claims 1-10, wherein the zinc oxide of (D) has a dimensional ratio (B/a) between peak a of 370nm to 390nm and peak B of 450nm to 600nm of 0.01 to 1 when photoluminescence is measured.
12. The thermoplastic resin composition of any one of claims 1 to 11, further comprising (E) an acrylate rubber-modified vinyl-based graft copolymer.
13. The thermoplastic resin composition of claim 12, wherein the weight ratio of (E) the acrylate rubber modified vinyl graft copolymer and (a) the polyalkyl (meth) acrylate resin is from 1:1.5 to 1:4.
14. The thermoplastic resin composition according to any one of claims 1 to 13, wherein at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, and dyes is further added.
15. A molded product manufactured from the thermoplastic resin composition according to any one of claims 1 to 14.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0013589 | 2021-01-29 | ||
| KR1020220012723A KR20220110121A (en) | 2021-01-29 | 2022-01-27 | Thermoplastic resin composition and molded product using the same |
| KR10-2022-0012723 | 2022-01-27 | ||
| PCT/KR2022/001601 WO2022164263A1 (en) | 2021-01-29 | 2022-01-28 | Thermoplastic resin composition and molded article using same |
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| CN116917407A true CN116917407A (en) | 2023-10-20 |
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